1. Field of the Invention
The disclosed invention relates to an improved method for treating ethanol fermentation still bottoms and recovering useful products there from. More specifically, this invention advantageously separates the solid and liquid residues while pasteurized by pressure across membrane filters in sanitary conditions with the permeate retaining low molecular weight minerals and nutrients at low to almost no concentration to make a unique non-alcoholic beverage or clean water for reuse in the process. Further, the means is unique and advantageous for the separated still bottom solids to be simultaneously concentrated for anaerobic digestion to produce fuels at a remote location and to have beneficial properties recovered before anaerobic digestion thereby producing chemicals, nutrients and medicinals.
2. Prior Art
Most of the 4000 alcohol distilleries in the world use starch and sugar feedstock up to 20% concentration in water for ethanol yeast fermentation that is heated to boiling in a column or pot still to evaporate the volatile fermentation products, mostly azeotropic ethanol, that condense in a column separator and the residuals are discharged as hot still bottoms that can contain from 1-10% inorganic and organic dissolved and suspended solids composed mostly of spent yeast cells and cell parts, metabolites, fermentation by-products, and non- fermentable starch and sugar feedstock residues. Distillation can also occur at lesser temperatures and lower pressures as in vacuum distillation. Nitrogen is often added to culture yeast before fermentation and typical yeast is composed of nearly 90% protein and carbohydrates. Following distillation this distilled fermentation water is often discharged directly to a water course, decanted into heavier and lighter fractions, or is evaporated to recover the solids as animal feed, filtered to recover other fermentation by-products from a concentrate, or biologically treated by anaerobic digestion to recover methane fuels. There are no unit methods known or found in the related art where discharged still bottoms are first pressure filtered in their pasteurized state with potable water recovered for human consumption and beneficial properties of the solid concentrate recovered before the remaining solids are sent to a anaerobic bioreactor that recovers methane to power the pressurized membrane filtration in an energy efficient process.
Pressure filtrations are most frequently used in the agricultural and food processing industry to concentrate solid and separate liquid fractions through porous membranes. For example, in U.S. Pat. No. 4,959,237 by Walker, a series of reverse osmosis units are used to concentrate fruit juice to improve the product quality and in U.S. Pat. No. 4,001,198 by Thomas, ultrafiltration is used to concentrate and pasteurize cheese whey nutrients. In Walker's invention, the permeate is recycled back to reverse osmosis and in Thomas' invention the permeate is discharged. In neither case is the permeate used as potable water and pasteurization is required in Thomas' to maintain sanitary condition of the concentrate. In U.S. Pat. No. 5,250,182, Bento et al invent a plurality of membrane based processes following centrifugation including microfiltration, ultrafiltration, nanofiltration and reverse osmosis to recover lactic acid and glycerol from a corn thin stillage stream following industrial ethanol fermentation and distillation that obviates the need for evaporation to concentrate syrup and produce lactic acid-free and glycerol-free animal feed upon drying with a filtration permeate that produces mineral free water to recycle as makeup water to the ethanol fermentation zone or as boiler water make-up. Bento et al's light stillage filtration invention means not to produce methane through anaerobic fermentation of the concentrate for an energy efficient pressurized filtration and means not to produce a nutrient water under sanitary conditions from pasteurized permeate for human consumption. Similarly, in U.S. Pat. No. 5,032,265 Kampen uses centrifugation and microfiltration first to preferentially remove coarse solids from stillage before subjecting the concentrate and permeate streams to a series of evaporation and ion exchange processes to recover distillers dried grain and solubles and glycerol, succinic and lactic acid. Kampen does not recover solids for methane gas production and rejects water as evaporate rather than recovering it.
Still bottoms can contain a wide range of insoluble and soluble solids in particulate and dissolved state that require removal before a pure potable water can be produced. Evaporation can separate non-volatile and suspended solids from a liquid condensate and centrifugation can separate suspended solids to approximately 1 micron from a liquid stream. Microfiltration can further separate coarse particles to between 10 and 0.1 microns, ultrafiltration finer particles and colloids sized to between 0.1 to 0.005 microns, nanofiltration particles and high molecular weight molecules to between 0.005 and 0.001 microns, and reverse osmosis particles and molecules to 0.00005 microns. Generally, microfiltration has a molecular weight cutoff of 0.1 million Daltons, ultrafiltration a molecular weight cutoff of 10,000 Daltons, nanofiltration 700 Daltons and reverse osmosis a molecular weight cutoff of 50-100 Daltons. Pressurized membrane assemblies can be tubular, hollow-fiber, spiral-wound, or flat plate with inlet pressures 40 bars or greater most often used. Spiral wound cross-flow filters are most efficient. Membranes for use at high temperatures are manufactured of the polyamide type.
As disclosed in the treatment of a sugar and starch wastewater, U.S. Pat. No. 6,036,854 to J. Potter, a concentration process using ultrafiltration is positioned at the front of a treatment system to convey the concentrates to a mixing tank for hydrolyzing the starch to sugars and adding nutrients to form a feedstock to a fermentation tank that grows yeast cells. However, the permeate from the ultrafiltration is discharged to the sewer and is not beneficially used.
As disclosed in U.S. Pat. No. 6,423,236 to Shiota, et al., a reverse osmosis system is used following wet-oxidation of organic wastewaters at high temperatures to separate molecules into the concentrate stream with acetic acid salts preferentially being the molecular weight of the concentrate cut off produced in the energy intensive wet oxidation process. In the preferred embodiment, Shiota, et al., suggest food processing wastes among many others as one possible organic source, option for elimination of wet-oxidation, and a non-descriptive anaerobic fermentation of the concentrate and household water use of the permeate from the reverse osmosis system. However, Shiota et al., make no specific claims to anaerobic fermentation or type in their invention, use of any methane gas to power the pressurized filtration system, recovering ammonia from the anaerobic fermentation to adjust pH before reverse osmosis, claim a temperature of 40 Celsius or below in reverse osmosis and a minimum concentration of 30 weight percent of an oxidizable substance as feedstock. For pasteurization to be in effect (70 Celsius for 30 minutes) would require a hot wet oxidation pre-treatment of this concentrated waste using the Shiota et al process before separation by reverse osmosis. Shiota, et al., therefore do not address the combined conditions necessary to separate fermentation still bottoms or many other similar food processing wastes by ultrafiltration or reverse osmosis before anaerobic digestion and to treat the concentrate by anaerobic digestion to recover energy to produce potable water for human consumption. The Shiota et al., process is disadvantageous to still bottom discharges because its descriptive specifications of concentration and temperature thresholds do not match those of fermentation still discharges or specific anaerobic fermentation processes and it would not be cost effective to adjust those parameters by further concentration, dilution and cooling not specified or disclosed.
Conventioanl anaerobic fermentation to produce methane gas is a mixed culture microbial process of liquefaction, acidogenisis and methanogenisis. Shiota et al., is using an energy intensive physical chemical process of wet-oxidation of organic wastewaters followed by reverse osmosis and is not descriptive of and is deficient in the specifications for a pressurized filtration system before anaerobic digestion to separate solids and liquids in an energy efficient and sanitary process without wet-oxidation.
Methanogenic bacteria are strictly anaerobic and die in the presence of oxygen. Unlike aerobic bacteria that convert its feedstock into microbial biomass and carbon dioxide through oxygen respiration, anaerobic bacteria convert its feedstock primarily into methane gas by a metabolic transfer of hydrogen. Methanogenisis is descriptive of an efficient biofuel cell process. Conventional anaerobic fermentation of concentrated organic wastes, particularly fermentation distillery discharges, use a variety of methods to increase the rate of degradation in order to decrease the size of the reactor and improve efficiency. Liquefaction (hydrolysis) and methanogenisis are rate limiting when performed together and hydraulic retention times toward 20 days and loading rates much less than 10 kg COD/cubic meter-day are often required for the mixed bacterial cultures to work efficiently together. Because the methanogenic bacteria are slow in reproductive growth rates and are sensitive to pH, they are most often rate limiting in the presence of an excess of fermentable acids, such as acetic and proprionic acids. For example, if hydrolysis occurs more rapidly than the slower methanogenisis, a build up of acidic conditions can occur and destroy the methanogenic bacteria. On the other hand, if the waste contain recalcitrant organics, hydrolysis will occur slowly limiting the feedstock for the methanogenic process. Various process control factors are used to improve efficiency of methanogenisis, including increasing mean cell residence times, separating hydrolysis and acidification from methanogenisis and increasing reaction rates by increasing temperatures that in turn culture a different and more efficient mixed bacterial culture.
Anaerobic lagoons, continuously stirred tank reactors (CSTR), CSTR's operated in contact mode, anaerobic filters, upflow anaerobic sludge blanket reactors (UASB), anaerobic fluidized bed reactors, and expanded bed reactors are among the technologies used for the distillery industry. The UASB reactor enhances reaction rate by increasing mean cell residence times by recirculating within the reactor granular particles and bacterial flocs that float on the surface that separates the reaction locations of acidification (5 days) and methanogenisis (7 days) in the reactor (see U.S. Pat. No. 5,773,526, Van Dijk, et al). The UASB method is sometimes dependent on preventing interfering flocs and too high of a strength of organic and suspended solids can inhibit reactions, often times requiring dilution. Though studied to operate in thermophilic mode (50-65 Celsius), reaction rates tend to be greater and interfere with floc formation. UASB systems are frequently used on distillery wastewaters and research has shown loading rates when operating in thermophilic mode of 16 kg of COD per cubic meter-day with 90% destruction for cane sugar distillery discharges. UASB systems can not operate at high suspended solids loadings.
CSTR reactors are conventional anaerobic digesters for high suspended solids loading and the hydraulic and mean cell residence times are about the same. The mean residence time of cells can be increased by separating cells from discharge and recirculating in contact mode. Studies of high concentration agricultural wastes operating in thermophilic contact mode at 8 day retentions have shown loading rates of 9 kg COD/cubic meter-day with 75% destruction and improved performance in thermophilic over mesophilic in destroying COD and enhancing the rate of liquefaction and methanogenisis. Compared to a CSTR system that doubles the solids concentration before anaerobic digestion, the UASB system exposes over 50% more water to bacterial degradation and consequently discharges a greater volume from the digester for waste management.
Pressurized membrane systems are used to refine and produce drinking water from wastewater. In U.S. Pat. No. 6,368,849, Norddahl invents a CSTR anaerobic fermentation process that recovers energy to power an ultrafiltration and denitrification device. Norddahl's ultrafiltration device is placed after anaerobic bacteria consume organic wastes. This process is disadvantageous if applied to fermentation still bottoms for beneficial drinking water recovery because there would be no separation of the beneficial characteristics of the pasteurized still bottoms into the permeate before bacterial degradation and contact. Nitrogen is recovered as aqueous ammonia for use as a fertilizer. In U.S. Pat. No. 5,374,356 Miller et al invent a ultrafiltration and nanofiltration device for treating wastewaters, particularly gray water, in closed environments such as ships for conserving and recycling the permeate as potable water. The invention is disadvantageous as it means not to produce methane through anaerobic fermentation of the concentrate for an energy efficient pressurized filtration and means not to produce a potable water under sanitary conditions from pasteurized feedstock for human consumption.
There are many beneficial properties to fermentation still bottoms including industrial, medicinal, nutritional, or commercial chemical product uses including when reprocessed further to simple chemical monomers. For example, a combination of cellulase and xylanase enzyme preparations to distillers dried grains solubles (DDGS) releases 96% of the glucose, 50% of the xylose, and 54% of the arabinose in DDGS carbohydrates (DOE Grant #DE-FG36-04GO14220, 1999). Though reports show means to enzymatically convert these carbohydrates to sugars, they do not show an industrial application to produce the carbohydrates and recover these sugars as this invention embodies. The sugars below 700 Dalton in molecular weight can be separated by membrane technology into a permeate, with the higher molecular weight residuals subjected to anaerobic digestion. Medicinal properties of fermentation include resveratrol, a well known anti-oxidant found in grapes and other plants. Resveratrol is found to be released from grapes by fermentation into wine and to be a cancer chemopreventative agent in mammals, including humans. In U.S. Pat. No. 6,861,085 Melwitz et al, describe a process for preparing a concentrate containing red wine extract and in U.S. Pat. No. 6,008,260 Pezzuto et al describe a solvent extraction procedure for isolating resveratrol. In the distillation of wine to make brandy, resveratrol with a molecular weight of 230 Dalton, would be present in the still bottoms and the concentrate fraction of reverse osmosis together with other minerals, nutrients and chemicals. There are no known processes that isolate and concentrate resveratrol from brandy stillage nor are there beverages derived from fermentation still bottoms that deliver these beneficial properties to a consumer.
Fermentation still bottoms can occur after a first membrane separation of solids and then a removal of ethanol from the liquid stream. For example, in U.S. Pat. No. 4,999,209 Gnekow removes volatile substances including alcohol from wine through a double reverse osmosis process and Weiss in U.S. Pat. No. 4,812,232 separately removes wine solids by reverse osmosis and then ethanol by vacuum distillation. In U.S. Pat. No. 4,988,525, Gresch uses a a diaphragm solids separation device followed by column distillation of ethanol. The objective is to make a non-alcoholic wine by recombining the wine concentrates with the liquid after the alcohol removed or separate the volatile acids from the alcohol before adding purified alcohol back to wine concentrate with makeup water. Potable water from fermentation still bottoms by solids removal is not the objective of these applications where solid removal is to concentrate wine solids first before the removal of ethanol from the volatile organic liquid stream.
Pressurized membrane systems are used to manufacture a water of beneficial character for commercial retail sales. The bottled water retail market is over $45 billion. There is a consumer demand for bottled water as a beverage because the source, process and composition is known and reliable and specific sealed and labeled sources containing nutrients or nutritious sources are more valuable to a health conscious consumer than bottled water from a generic source. Bottled water is frequently marketed and labeled as reverse osmosis or ultrafiltered water to gain acceptance that it has been treated and additives are often introduced to enhance nutritional value, color, odor and taste. With groundwater contamination, air pollution fallout and runoff into water bodies, spring water and river waters are becoming less reliable sources. There is a limited product on the market where bottled water is obtained directly from the feedstock of a pasteurized source and there are limited, if any, beverages known on the market derived directly from the filtration of fermentation still bottoms, or that also contain the natural nutrients and medicinals of fermentation still bottoms.